CN113860860A - 一种高效环保的锂电正极材料用匣钵及其制备方法 - Google Patents

一种高效环保的锂电正极材料用匣钵及其制备方法 Download PDF

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CN113860860A
CN113860860A CN202111253925.3A CN202111253925A CN113860860A CN 113860860 A CN113860860 A CN 113860860A CN 202111253925 A CN202111253925 A CN 202111253925A CN 113860860 A CN113860860 A CN 113860860A
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余俊
孙子恒
张寒
赵惠忠
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Wuhan University of Science and Engineering WUSE
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Abstract

本发明涉及一种高效环保的锂电正极材料用匣钵及其制备方法。其技术方案是:以3~28wt%的钛铝酸钙细粉、30~55wt%的莫来石颗粒、10~20wt%的堇青石颗粒、7~11wt%的α‑氧化铝微粉、9~14wt%的滑石细粉和9~15wt%的广西白泥细粉为原料,外加所述原料3~4wt%的纸浆废液,搅拌5~8min,封装困料12~24h;再于100~150MPa条件下机压成型,在90~110℃条件下干燥12~24h,然后于1300℃~1400℃条件下保温3~4h,制得高效环保的锂电正极材料用匣钵。本发明具有成本低廉、工艺简单和绿色环保的特点;所制备的高效环保的锂电正极材料用匣钵体不仅具有优良的力学性能、热震稳定性和抗侵蚀性能,且体积密度高、抗折耐压强度大和使用寿命长。

Description

一种高效环保的锂电正极材料用匣钵及其制备方法
技术领域
本发明属于锂电正极材料用匣钵技术领域。具体涉及一种高效环保的锂电正极材料用匣钵及其制备方法。
背景技术
近年来,锂离子电池作为绿色环保的新能源电池,大量应用于新能源汽车和储能领域,并取得了高速发展。锂离子电池最为核心和昂贵的材料就是正极材料,锂离子电池性能的好坏与正极材料品质的优劣息息相关。当前,锂离子电池正极材料的制备方法主要是高温固相合成法,首先将制备正极材料所需原料通过机械搅拌、球磨或压片等方式混合均匀,然后通过将原料承载在匣钵中并置于窑炉中通过高温煅烧,保温及冷却后再进行破碎、研磨和过筛。
在制备锂离子电池正极材料的过程中,匣钵的使用性能尤为关键,高品质匣钵需要优良的力学性能、热震稳定性和抗侵蚀性能。然而目前锂离子电池正极材料的生产中主要使用的匣钵为莫来石-堇青石质匣钵,即使用莫来石-堇青石复相耐火材料制备匣钵,虽然力学性能及热震稳定性良好,但抗侵蚀性能差。故制备具有优良的力学性能、热震稳定性及抗侵蚀性能的高品质匣钵为本领域技术人员所关注的热点之一。
如文献(陈宁,李素平,丁颖颖等.烧成工艺对堇青石-莫来石窑具材料性能的影响[J].中国陶瓷,2017,53(1):86~90.)报道,将莫来石熟料及堇青石熟料作为骨料进行混合,于1370℃保温3小时,烧结出莫来石-堇青石质材料,其力学性能及热震稳定性虽好,但抗侵蚀性差,所以一般作为普通窑具使用。
又如文献(黄宏,黄朝晖,房明浩等.LiCoO2合成过程对镁铝尖晶石陶瓷侵蚀的研究[J].硅酸盐通报,2011,30(3):515-518.)报道,氧化镁或镁铝尖晶石虽对锂离子电池正极材料具有良好的抗侵蚀性能,但镁铝尖晶石抗热震性能不好,难以保证锂离子电池匣钵的使用寿命。
再如文献(Dafei Dinga,Guotian Yea,Liugang Chena.Superior corrosionresistance KAlSi2O6-containing materials for calcining Li-ion battery cathodematerials[J].Corrosion Science,2019,157:324~330.)报道,公开了一种用KAlSi2O6层包裹莫来石颗粒的方法,通过预制或原位生成KAlSi2O6形成一种防侵蚀屏障,提高其耐侵蚀性,但是力学性能差且原料成本过高,工艺复杂,不利于规模化生产。
发明内容
本发明旨在克服现有技术缺陷,目的在于提供一种成本低廉、工艺简单的高效环保的锂电正极材料用匣钵的制备方法,用该方法制备的高效环保的锂电正极材料用匣钵具有优良的力学性能、热震稳定性和抗侵蚀性能,使用寿命长。
为实现上述目的,本发明采用的技术方案是:
以3~28wt%的钛铝酸钙细粉、30~55wt%的莫来石颗粒、10~20wt%的堇青石颗粒、7~11wt%的α-氧化铝微粉、9~14wt%的滑石细粉和9~15wt%的广西白泥细粉为原料,外加所述原料3~4wt%的纸浆废液,搅拌5~8min,封装困料12~24h;再于100~150MPa条件下机压成型,于90~110℃条件下干燥12~24h,然后于1300℃~1400℃条件下保温3~4h,制得高效环保的锂电正极材料用匣钵。
所述钛铝酸钙细粉的主要化学成分是:Al2O3含量≥74.18wt%,CaO含量≥11.69wt%,TiO2含量≥11.08wt%,Fe2O3含量≥1.03wt%,MgO含量≤1.51wt%,SiO2含量≤0.42wt%;所述钛铝酸钙细粉的粒度≤0.074mm。
所述莫来石颗粒的主要化学成分是:Al2O3含量≥67.66wt%,SiO2含量≥27.00wt%,Fe2O3含量≥1.01wt%;所述莫来石颗粒的粒度≤1.000mm。
所述堇青石颗粒的主要化学成分是:Al2O3含量≥36.35wt%,SiO2含量≥44.33wt%,MgO含量≥14.29wt%;所述堇青石颗粒的粒度≤1.000mm。
所述α-氧化铝微粉的Al2O3含量≥99.50wt%;所述α-氧化铝微粉的粒度≤0.058mm。
所述滑石细粉的主要化学成分是:SiO2含量≥51.35wt%,MgO含量≥28.72wt%;所述滑石细粉的粒度≤0.088mm。
所述广西白泥的主要化学成分是:Al2O3含量≥35.36wt%,SiO2含量≥48.14wt%;所述广西白泥的粒度≤0.088mm。
由于采用上述技术方案,本发明与现有技术相比具有以下优点:
1、本发明以钛铝酸钙细粉、莫来石颗粒、堇青石颗粒、α-氧化铝微粉、滑石细粉和广西白泥细粉为原料,外加纸浆废液,搅拌,困料,机压成型,干燥,在1300℃~1500℃条件下烧成,制得高效环保的锂电正极材料用匣钵(以下简称匣钵),不仅原料来源广泛,生产成本低,且工艺简单。
2、本发明采用的原料钛铝酸钙为生产钛铁合金过程中产生的废渣,不仅节约资源,且能减少污染,绿色环保,具有显著的经济效益和社会效益。
3、本发明利用钛铝酸钙的多相性,如钛铝酸钙与其它含硅原料在高温下容易生成钙长石,钙长石作为嵌入相能阻止锂离子电池正极材料的渗透,能显著提升匣钵的抗侵蚀性能和使用寿命。又如钛铝酸钙在高温下析出游离的氧化钛,起到增韧效果,能有效提高匣钵的力学性能。
4、本发明采用的钛铝酸钙具有高的熔点、高的耐火度和低的热膨胀系数等,能有效提高匣钵的热震稳定性。
本发明所制备的高效环保的锂电正极材料用匣钵经检测:体积密度为2.18~2.60g·cm-3;显气孔率为18.2~23.6%;抗折强度为8.2~20.4MPa;耐压强度为75.9~148.4MPa;热震(ΔT=1100℃,水冷3次)后的抗折强度保持率为39~56%。
因此,本发明具有成本低廉、工艺简单和绿色环保的特点;所制备的高效环保的锂电正极材料用匣钵体不仅具有优良的力学性能、热震稳定性和抗侵蚀性能,且体积密度高、抗折耐压强度大和使用寿命长。
具体实施方式
下面结合具体实施方式对本发明作进一步的描述,并非对其保护范围的限制。
为避免重复,先将本具体实施方式所涉及的物料统一描述如下,实施例中不再赘述:
所述钛铝酸钙细粉的主要化学成分是:Al2O3含量≥74.18wt%,CaO含量≥11.69wt%,TiO2含量≥11.08wt%,Fe2O3含量≥1.03wt%,MgO含量≤1.51wt%,SiO2含量≤0.42wt%;所述钛铝酸钙细粉的粒度≤0.074mm。
所述莫来石颗粒的主要化学成分是:Al2O3含量≥67.66wt%,SiO2含量≥27.00wt%,Fe2O3含量≥1.01wt%;所述莫来石颗粒的粒度≤1.000mm。
所述堇青石颗粒的主要化学成分是:Al2O3含量≥36.35wt%,SiO2含量≥44.33wt%,MgO含量≥14.29wt%;所述堇青石颗粒的粒度≤1.000mm。
所述α-氧化铝微粉的Al2O3含量≥99.50wt%;所述α-氧化铝微粉的粒度≤0.058mm。
所述滑石细粉的主要化学成分是:SiO2含量≥51.35wt%,MgO含量≥28.72wt%;所述滑石细粉的粒度≤0.088mm。
所述广西白泥的主要化学成分是:Al2O3含量≥35.36wt%,SiO2含量≥48.14wt%;所述广西白泥的粒度≤0.088mm。
实施例1
一种高效环保的锂电正极材料用匣钵及其制备方法。本实施例所述制备方法是:
以3~10wt%的钛铝酸钙细粉、45~55wt%的莫来石颗粒、10~12wt%的堇青石颗粒、9~11wt%的α-氧化铝微粉、11~14wt%的滑石细粉和12~15wt%的广西白泥细粉为原料,外加所述原料3~3.5wt%的纸浆废液,搅拌5~6.5min,封装困料12~15h;再于100~115MPa条件下机压成型,于90~100℃条件下干燥12~15h,然后在1300~1350℃条件下保温3~3.5h,制得高效环保的锂电正极材料用匣钵。
本实施例所制备的高效环保的锂电正极材料用匣钵经检测:体积密度为2.18~2.37g·cm-3;显气孔率为21.2~23.6%;抗折强度为14.5~20.3MPa;耐压强度为111.2~148.4MPa;热震(ΔT=1100℃,水冷3次)后强度保持率为51~56%。
实施例2
一种高效环保的锂电正极材料用匣钵及其制备方法。本实施例所述制备方法是:
以10~16wt%的钛铝酸钙细粉、40~45wt%的莫来石颗粒、12~15wt%的堇青石颗粒、9~11wt%的α-氧化铝微粉、11~14wt%的滑石细粉和12~15wt%的广西白泥细粉为原料,外加所述原料3~3.5wt%的纸浆废液,搅拌5~6.5min,封装困料15~18h;再于115~130MPa条件下机压成型,于90~100℃条件下干燥15~18h,然后在1300~1350℃条件下保温3~3.5h,制得高效环保的锂电正极材料用匣钵。
本实施例所制备的高效环保的锂电正极材料用匣钵经检测:体积密度为2.24~2.41g·cm-3;显气孔率为20.0~22.7%;抗折强度为15.2~20.4MPa;耐压强度为102.5~144.4MPa;热震(ΔT=1100℃,水冷3次)后强度保持率为45~53%。
实施例3
一种高效环保的锂电正极材料用匣钵及其制备方法。本实施例所述制备方法是:
以16~23wt%的钛铝酸钙细粉、35~40wt%的莫来石颗粒、15~17wt%的堇青石颗粒、7~9wt%的α-氧化铝微粉、9~11wt%的滑石细粉和9~12wt%的广西白泥细粉为原料,外加所述原料3.5~4wt%的纸浆废液,搅拌6.5~8min,封装困料18~21h;再于130~140MPa条件下机压成型,于100~110℃条件下干燥18~21h,然后在1350~1400℃条件下保温3.5~4h,制得高效环保的锂电正极材料用匣钵。
本实施例所制备的高效环保的锂电正极材料用匣钵经检测:体积密度为2.34~2.52g·cm-3;显气孔率为19.5~21.2%;抗折强度为12.3~18.7MPa;耐压强度为88.1~123.7MPa;热震(ΔT=1100℃,水冷3次)后强度保持率为42~49%。
实施例4
一种高效环保的锂电正极材料用匣钵及其制备方法。本实施例所述制备方法是:
以23~28wt%的钛铝酸钙细粉、30~35wt%的莫来石颗粒、17~20wt%的堇青石颗粒、7~9wt%的α-氧化铝微粉、9~11wt%的滑石细粉和9~12wt%的广西白泥细粉为原料,外加所述原料3.5~4wt%的纸浆废液,搅拌6.5~8min,封装困料21~24h;再于140~150MPa条件下机压成型,于100~110℃条件下干燥21~24h,然后在1350~1400℃条件下保温3.5~4h,制得高效环保的锂电正极材料用匣钵。
本实施例所制备的高效环保的锂电正极材料用匣钵经检测:体积密度为2.45~2.60g·cm-3;显气孔率为18.2~20.3%;抗折强度为8.2~14.9MPa;耐压强度为75.9~110.2MPa;热震(ΔT=1100℃,水冷3次)后强度保持率为39~45%。
本具体实施方式与现有技术相比具有以下积极效果:
1、本具体实施方式以钛铝酸钙细粉、莫来石颗粒、堇青石颗粒、α-氧化铝微粉、滑石细粉和广西白泥细粉为原料,外加纸浆废液,搅拌,困料,机压成型,干燥,在1300℃~1500℃条件下烧成,制得高效环保的锂电正极材料用匣钵(以下简称匣钵),不仅原料来源广泛,生产成本低,且工艺简单。
2、本具体实施方式采用的原料钛铝酸钙为生产钛铁合金过程中产生的废渣,不仅节约资源,且能减少污染,绿色环保,具有显著的经济效益和社会效益。
3、本具体实施方式利用钛铝酸钙的多相性,如钛铝酸钙与其它含硅原料在高温下容易生成钙长石,钙长石作为嵌入相能阻止锂离子电池正极材料的渗透,能显著提升匣钵的抗侵蚀性能和使用寿命。又如钛铝酸钙在高温下析出游离的氧化钛,起到增韧效果,能有效提高匣钵的力学性能。
4、本具体实施方式采用的钛铝酸钙具有高的熔点、高的耐火度和低的热膨胀系数等,能有效提高匣钵的热震稳定性。
本具体实施方式所制备的高效环保的锂电正极材料用匣钵经检测:体积密度为2.18~2.60g·cm-3;显气孔率为18.2~23.6%;抗折强度为8.2~20.4MPa;耐压强度为75.9~148.4MPa;热震(ΔT=1100℃,水冷3次)后的抗折强度保持率为39~56%。
因此,本具体实施方式具有成本低廉、工艺简单和绿色环保的特点;所制备的高效环保的锂电正极材料用匣钵体不仅具有优良的力学性能、热震稳定性和抗侵蚀性能,且体积密度高、抗折耐压强度大和使用寿命长。

Claims (8)

1.一种高效环保的锂电正极材料用匣钵的制备方法,其特征在于所述制备方法是:以3~28wt%的钛铝酸钙细粉、30~55wt%的莫来石颗粒、10~20wt%的堇青石颗粒、7~11wt%的α-氧化铝微粉、9~14wt%的滑石细粉和9~15wt%的广西白泥细粉为原料,外加所述原料3~4wt%的纸浆废液,搅拌5~8min,封装困料12~24h;再于100~150MPa条件下机压成型,于90~110℃条件下干燥12~24h,然后于1300℃~1400℃条件下保温3~4h,制得高效环保的锂电正极材料用匣钵。
2.根据权利要求1所述的高效环保的锂电正极材料用匣钵的制备方法,其特征在于所述钛铝酸钙细粉的主要化学成分是:Al2O3含量≥74.18wt%,CaO含量≥11.69wt%,TiO2含量≥11.08wt%,Fe2O3含量≥1.03wt%,MgO含量≤1.51wt%,SiO2含量≤0.42wt%;所述钛铝酸钙细粉的粒度≤0.074mm。
3.根据权利要求1所述的高效环保的锂电正极材料用匣钵的制备方法,其特征在于所述莫来石颗粒的主要化学成分是:Al2O3含量≥67.66wt%,SiO2含量≥27.00wt%,Fe2O3含量≥1.01wt%;所述莫来石颗粒的粒度≤1.000mm。
4.根据权利要求1所述的高效环保的锂电正极材料用匣钵的制备方法,其特征在于所述堇青石颗粒的主要化学成分是:Al2O3含量≥36.35wt%,SiO2含量≥44.33wt%,MgO含量≥14.29wt%;所述堇青石颗粒的粒度≤1.000mm。
5.根据权利要求1所述的高效环保的锂电正极材料用匣钵的制备方法,其特征在于所述α-氧化铝微粉的Al2O3含量≥99.50wt%;所述α-氧化铝微粉的粒度≤0.058mm。
6.根据权利要求1所述的高效环保的锂电正极材料用匣钵的制备方法,其特征在于所述滑石细粉的主要化学成分是:SiO2含量≥51.35wt%,MgO含量≥28.72wt%;所述滑石细粉的粒度≤0.088mm。
7.根据权利要求1所述的高效环保的锂电正极材料用匣钵的制备方法,其特征在于所述广西白泥的主要化学成分是:Al2O3含量≥35.36wt%,SiO2含量≥48.14wt%;所述广西白泥的粒度≤0.088mm。
8.一种高效环保的锂电正极材料用匣钵,其特征在于所述高效环保的锂电正极材料用匣钵是根据权利要求1~7项中任一项所述的高效环保的锂电正极材料用匣钵的制备方法所制备的高效环保的锂电正极材料用匣钵。
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